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yields the same relative increase in temperature driving force. However, the interface vapor pressure can only approach the limit of zero. Because of this, for equal molecular and thermal diffusivities a saturated mixture will supersaturate when cooled. The tendency to supersaturate generally increases with increased molecular weight of the condensable, increased temperature differences, and reduced initial superheating. To evaluate whether a given condensing step yields fog requires rigorous treatment of the coupled heat-transfer and masstransfer processes through the entire condensation. Steinmeyer [Chem. Eng. Prog., 68(7), 64 (1972)] illustrates this, showing the impact of foreign-nuclei concentration on calculated fog formation. See Table 14-21. Note the relatively large particles generated for cases 1 and 2 for 10,000 foreign nuclei per cm3. These are large enough to be fairly easily collected. There have been very few documented problems with industrial condensers despite the fact that most calculate to generate supersaturation along the condensing path. The explanation appears to be a limited supply of foreign nuclei.

Ryan et al. [Chem. Eng. Progr., 90(8), 83 (1994)] show that separate mass and heat transfer-rate modeling of an HCl absorber predicts 2 percent fog in the vapor. The impact is equivalent to lowering the stage efficiency to 20 percent.

Spontaneous (Homogeneous) Nucleation This process is quite difficult because of the energy barrier associated with creation of the interfacial area. It can be treated as a kinetic process with the rate a very steep function of the supersaturation ratio (S = partial pressure of condensable per vapor pressure at gas temperature). For water, an increase in S from 3.4 to 3.9 causes a 10,000-fold increase in the nucleation rate. As a result, below a critical supersaturation (Sorit), homogeneous nucleation is slow enough to be ignored. Generally, Scrit is defined as that which limits nucleation to one particle produced per cubic centimeter per second. It can be estimated roughly by traditional theory (Theory of Fog Condensation, Israel Program for Scientific Translations, Jerusalem, 1967) using the following equation:

Scrit = exp

where C = surface tension, mN/m (dyn/cm) pi = liquid density, g/cm3 T = temperature, K M = molecular weight of condensable

Table 14-22 shows typical experimental values of Scrit taken from the work of Russel [J. Chem. Phys., 50, 1809 (1969)]. Since the critical supersaturation ratio for homogeneous nucleation is typically greater

TABLE 14-22 Experimental Critical Supersaturation Ratios
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